CN116003164B - Method for improving binding force between C/C composite material matrix and SiC coating - Google Patents
Method for improving binding force between C/C composite material matrix and SiC coating Download PDFInfo
- Publication number
- CN116003164B CN116003164B CN202211627507.0A CN202211627507A CN116003164B CN 116003164 B CN116003164 B CN 116003164B CN 202211627507 A CN202211627507 A CN 202211627507A CN 116003164 B CN116003164 B CN 116003164B
- Authority
- CN
- China
- Prior art keywords
- composite material
- sic
- deposition
- coating
- sic coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000011159 matrix material Substances 0.000 title abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 53
- 239000002070 nanowire Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 32
- 239000004917 carbon fiber Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract 2
- 230000008021 deposition Effects 0.000 claims description 52
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 19
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 17
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 244000137852 Petrea volubilis Species 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 11
- 238000004321 preservation Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 14
- 239000011258 core-shell material Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000005245 sintering Methods 0.000 description 14
- 239000011812 mixed powder Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000002679 ablation Methods 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- BKXAWQXZFFNQHY-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] BKXAWQXZFFNQHY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for improving the binding force between a C/C composite material matrix and a SiC coating, which comprises the following steps: C/C composite pre-oxidation treatment; soaking the preoxidized C/C composite material in an ethanol solution of a metal salt catalyst to load the catalyst, and then placing the catalyst in powder (SiO with the mass percentage of 1:0.1-0.6:0.2-0.8) 2 Mixture of Si and C powder) are heated to 1200-1800 ℃ together, and cooled to room temperature after heat preservation, thereby constructing a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material; (3) And depositing a SiC coating on the C/C composite material by adopting low-pressure chemical vapor deposition at 900-1500 ℃. The invention effectively designs a matrix-coating multi-scale mechanical linkage structure and obtains the nanowire which grows in situ and directionally, and toughens the SiC coating while improving the interface combination between the SiC coating and the C/C composite material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a method for improving the binding force of a C/C composite material matrix and a SiC coating based on a multi-scale core-shell structure of a carbon fiber cone@directional SiC nanowire.
Background
The carbon/carbon (C/C) composite material has the characteristics of low density, low thermal expansion coefficient, excellent high-temperature mechanical property and the like, and is considered as one of the most promising high-temperature structural materials in the fields of aerospace and national defense. However, the rapid oxidation and ablation of C/C composites in high temperature aerobic environments severely limits their wide application. Currently, coating technology is an effective approach to improve the oxidation/ablation resistance of C/C composites. Wherein, due to the close thermal expansion coefficient with the C/C matrix, good physical and chemical compatibility and high temperature, siO with self-healing capability and extremely low oxygen diffusion permeability can be generated 2 Vitreous protective films, siC coatings are widely used. Chemical Vapor Deposition (CVD) is a common technique for preparing SiC coatings, which generally requires lower preparation temperatures, thereby effectively avoiding thermal damage to the substrate, and which also yields coatings of higher density and purity. However, but generallyThe interface between the CVD-SiC coating and the C/C matrix is flat, so that strong chemical bonding cannot be formed, and the coating is easy to crack and peel in the high-low temperature alternating service process, so that the C/C composite material is invalid. Therefore, how to improve the compatibility with the C/C matrix and the interface binding force are important factors to consider for the stable service of the CVD-SiC coating.
The use of pre-oxidation to build a mosaic structure interface between a CVD-SiC coating and a C/C substrate improves the bond between the two to some extent, as described in documents 1"Shan YC,Fu QG,Li HJ,et al.Improvement of the bonding strength and the oxidation resistance of SiC coating on C/C composites by pre-oxidation treatment [ J ]. Surface and Coatings Technology,2014,253:234-240 ]. However, CVD-SiC coatings still tend to crack due to the inherent brittleness of the ceramic coating and poor load transfer effects caused by the single micron scale carbon fibers in the mosaic interlocking structure. The C/C oxidation pretreatment and the nanowire toughening are combined to construct the multi-scale nanowire-carbon fiber preform, so that the interface is expected to be further strengthened and the toughness of the CVD-SiC ceramic coating is expected to be improved. The SiC nanowire is considered as an ideal toughening phase of a ceramic material due to the characteristics of high strength, good thermal stability, excellent oxidation resistance and the like, and can effectively inhibit cracking of a coating. Document 2"Chu YH,Li HJ,Fu QG,et al.Oxidation protection of C/C composites with a multilayer coating of SiC and Si +sic+sic nanowires [ J ]. Carbon,2012, 50:1280-1288" randomly oriented SiC nanowire toughened Si-SiC coatings were prepared on C/C composite substrates using CVD processes. Although the technology relieves the cracking trend of the ceramic coating to a certain extent, the prepared SiC nanowire is paved on the surface of the matrix, so that the improvement effect of the interface binding force between the SiC nanowire and the matrix is limited, the load transmission effect is poor, and the toughening effect of the coating is limited. Meanwhile, the orientation of the SiC nanowires is also important for the toughening effect of the SiC nanowires. Thus, obtaining in-situ directionally grown SiC nanowires on the pre-oxidized substrate surface is critical to further improve C/C interface bonding with the coating and to increase coating toughness.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a method for improving the binding force of a C/C composite material matrix and a SiC coating based on a multi-scale core-shell structure of a carbon fiber cone@directional SiC nanowire. The method has the advantages of simple operation, controllable process, low raw material cost and good repeatability, effectively designs the matrix-coating multi-scale mechanical linkage structure, obtains the nanowire with in-situ directional growth, improves the interface combination between the SiC coating and the C/C composite material, toughens the SiC coating, and provides a new technology and method for improving the oxidation/ablation resistance of the C/C composite material.
The above object of the present invention is achieved by the following technical solutions:
a method for improving the binding force of a C/C composite substrate and a SiC coating, comprising:
1. C/C composite pre-oxidation treatment: firstly, siC sand paper is used to make the density of 1.75-1.85 g/cm 3 Polishing the C/C composite material, ultrasonically cleaning the C/C composite material for 10 to 70 minutes by using absolute ethyl alcohol and deionized water, and then placing the C/C composite material in an oven at 60 to 100 ℃ for 5 to 24 hours until the C/C composite material is dried. And (3) placing the dried C/C composite material into a resistance oxidation furnace at 600-1000 ℃, preserving heat for 2-10 min, taking out a pre-oxidized C/C sample, cooling to room temperature, and weighing for standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing an ethanol solution of a metal salt catalyst with the concentration of 0.1-2 mol/L by taking metal salt as a solute and ethanol as a solvent, placing the C/C sample pre-oxidized in the step one into the solution, soaking for 2-24 h, taking out, and drying for later use. SiO with the mass percentage of 1:0.1-0.6:0.2-0.8 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then weighing 1-10 g of the mixed powder, placing the mixed powder at the bottom of a graphite crucible, hanging a pre-oxidized C/C sample loaded with a catalyst above powder in the crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (flow is 10-200 mL/min), the temperature is raised to 1200-1800 ℃ at the heating rate of 5-10 ℃/min, the temperature is kept for 0.5-10 h, the power supply is turned off, and the sample is taken out after natural cooling to room temperature.
3. Low Pressure Chemical Vapor Deposition (LPCVD) process to make SiC coatings:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.1-0.4 Pa. Argon is introduced at a flow rate of 150-400 mL/min, and the furnace temperature is raised to 900-1500 ℃ at a heating rate of 5-10 ℃/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and then Methyl Trichlorosilane (MTS) is brought into the reaction zone by hydrogen in a bubbling mode for deposition. Wherein the flow rates of argon, hydrogen and MTS are respectively 150-500 mL/min, 300-800 mL/min and 300-800 mL/min during deposition, the pressure of the reactor is 3-10 kPa, and the deposition time is 0.5-10 h. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
Preferably, the metal salt used as the catalyst in the ethanol solution of the metal salt catalyst in the step one is one of the following, but is not limited to: iron nitrate, cobalt nitrate, nickel nitrate, ferrous sulfate, cobalt sulfate, nickel sulfate, ferric chloride, cobalt chloride and nickel chloride.
The invention prepares the C/C composite material coated carbon fiber cone@directional SiC nanowire core-shell structure toughened SiC coating through simple pre-oxidation and two-step CVD processes. The method effectively designs a matrix-coating multi-scale mechanical linkage structure and obtains the nanowire which grows in situ directionally, thereby providing a new technology and method for improving interface combination and coating toughness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
In the drawings:
FIG. 1 is a process flow diagram of the method of the present invention;
FIG. 2 is a surface topography of an original C/C composite material employed in the present invention;
FIG. 3 is a surface micrograph of a preoxidized C/C composite prepared according to example 1 of the present invention;
FIG. 4 is a microscopic morphology of a core-shell structure array of "carbon fiber cone @ oriented SiC nanowires" of a surface of a pre-oxidized C/C composite material prepared in accordance with example 1 of the present invention;
FIG. 5 is a microscopic topography of the fracture surface of a coated sample prepared according to example 1 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples for more clearly understood objects, technical solutions and advantages of the present invention.
The invention provides a method for improving the binding force of a C/C composite material matrix and a ceramic coating. Firstly, constructing a carbon fiber cone porous layer on the surface of a C/C composite material through a simple pre-oxidation and catalytic auxiliary CVD process, and further obtaining a large-area carbon fiber cone@directional SiC nanowire core-shell structure array; and finally preparing the C/C matrix wrapped carbon fiber cone@directional SiC nanowire multi-scale core-shell structure toughened SiC coating by combining an LPCVD process. According to the invention, a catalyst-assisted gas-liquid-solid (VLS) mechanism is adopted, the prepared SiC nanowire is obviously oriented on the whole surface of a single carbon fiber cone, the carbon fiber cone is taken as a core, a core-shell structure of the carbon fiber cone@oriented SiC nanowire is formed by in-situ uniform oriented growth, and the effect of large-area and repeatable in-situ oriented growth of the core-shell structure array is realized on the surface of a fiber cone porous layer. Compared with the SiC nanowires which are randomly oriented, the SiC nanowires which are directionally grown in situ generate nanoscale mechanical interlocking with the matrix, so that the load can be effectively transferred from the matrix to the nanowires, and the SiC nanowires are considered to have more excellent toughening effect. In addition, the invention effectively designs a matrix-coating multi-scale mechanical linkage structure and obtains the nanowire which grows in situ and directionally, improves the interface combination between the SiC coating and the C/C composite material and toughens the SiC coating, thereby providing a new technology and method for improving the oxidation/ablation resistance of the C/C composite material.
FIG. 1 is a process flow chart of the method for improving the binding force between a C/C composite material matrix and a ceramic coating, which clearly shows the preparation process proposed by the invention, wherein the preparation process mainly comprises 3 steps, including C/C composite material pre-oxidation treatment; the structure of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material; the SiC coating is prepared by an LPCVD method. As shown in the figure, the method of the invention is simple to operate, and the specific process will be described in the following examples.
Example 1:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.78g/cm 3 Polishing and ultrasonic cleaning with absolute ethanol and deionized water for 30min, and then placing the C/C composite material in an oven at 80 ℃ for 12h until the C/C composite material is dried. And (3) placing the dried C/C composite material in a resistance oxidation furnace at 900 ℃, preserving heat for 5min, taking out a pre-oxidized C/C sample, cooling to room temperature, and weighing for standby.
FIG. 2 shows the surface morphology of the original C/C composite material used in the present invention, and it can be seen that the interior is mainly composed of fiber/matrix interfaces, carbon fibers, carbon matrix, and a small number of defects. The carbon fiber is surrounded by pyrolytic carbon, and the pyrolytic carbon are tightly combined, so that no obvious interfacial separation phenomenon exists. FIG. 3 is a surface micrograph of a pre-oxidized C/C composite prepared according to this example. The macroscopic morphology change of the C/C composite material is shown as a significant increase in overall roughness. The microscopic morphology shows that the fiber and the matrix are subjected to serious oxidation damage, the surface matrix is basically oxidized completely, the residual quantity is small, only fiber cores distributed in a gap are left, the fiber ends are oxidized into needle-shaped shapes, and the diameter of the fiber ends is greatly reduced.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing ferric nitrate ethanol solution with the concentration of 1mol/L, placing the C/C sample pre-oxidized in the step one into the solution, soaking for 2 hours, taking out, and drying for later use. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then weighing 5g of the mixed powder, placing the mixed powder at the bottom of a graphite crucible, hanging a pre-oxidized C/C sample loaded with a catalyst above powder in the crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (flow is 50 mL/min), the temperature is raised to 1500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, and the sample is taken out after natural cooling to room temperature.
Fig. 4 is a microscopic morphology of a core-shell structure array of "carbon fiber cone @ oriented SiC nanowires" on the surface of the pre-oxidized C/C composite material prepared according to this example. As can be seen from the graph, the SiC nanowire prepared by the method is not only obviously oriented on the whole surface of a single carbon fiber cone, but also grows on the surface of the carbon fiber cone in situ in an approximately vertical direction, and a core-shell structure taking the carbon fiber cone as a core and the SiC nanowire as a shell is constructed. In addition, the SiC nanowires are uniformly distributed in the whole core-shell structure array, so that the effect of large-area and repeatable in-situ directional growth of the carbon fiber cone@directional SiC nanowire core-shell structure is realized.
3. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 200mL/min and the furnace temperature was raised to 1300 c at a heating rate of 5 c/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein, the flow rates of argon, hydrogen and MTS are respectively 500mL/min, 200mL/min and 200mL/min during deposition, the pressure of the reactor is 5.0kPa, and the deposition time is 2 hours. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
Fig. 5 is a microscopic morphology of the fracture surface of a coating specimen prepared according to this example, and significant nanowire extraction was observed. This is because the SiC coating attached to the nanowire increases the interfacial sliding resistance of the nanowire, so that the SiC nanowire needs to consume a certain amount of energy against the friction with the coating material during the pullout process, which is advantageous for improving the interfacial bonding strength of the coating.
Example 2:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.75g/cm 3 Polishing and ultrasonic cleaning with absolute ethanol and deionized water for 30min, and then placing the C/C composite material in an oven at 70 ℃ for 10h until the C/C composite material is dried. Will be driedPlacing the C/C composite material in a resistance oxidation furnace at 1000 ℃, preserving heat for 5min, taking out a preoxidized C/C sample, cooling to room temperature, and weighing for standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing ferric nitrate ethanol solution with the concentration of 0.8mol/L, placing the C/C sample pre-oxidized in the step one into the solution, soaking for 3 hours, taking out, and drying for later use. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then weighing 5g of the mixed powder, placing the mixed powder at the bottom of a graphite crucible, hanging a pre-oxidized C/C sample loaded with a catalyst above powder in the crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (flow is 100 mL/min), the temperature is raised to 1500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, the sample is naturally cooled to room temperature, and the sample is taken out.
3. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 150mL/min and the furnace temperature was raised to 1300 c at a heating rate of 5 c/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein, the flow rates of argon, hydrogen and MTS are 400mL/min, 200mL/min and 200mL/min respectively during deposition, the pressure of the reactor is 6.0kPa, and the deposition time is 2 hours. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
Example 3:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.80g/cm 3 Polishing and ultrasonic cleaning with absolute ethanol and deionized water for 25min, and then placing the C/C composite material in an oven at 60 ℃ for 8h until the C/C composite material is dried. Placing the dried C/C composite material in a resistance oxidation furnace at 800 ℃, preserving heat for 8min, taking out a preoxidized C/C sample, cooling to room temperature, and weighingAnd (5) standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing a cobalt nitrate ethanol solution with the concentration of 1mol/L, placing the C/C sample pre-oxidized in the step one into the solution, soaking for 2 hours, taking out, and drying for later use. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then weighing 5g of the mixed powder, placing the mixed powder at the bottom of a graphite crucible, hanging a pre-oxidized C/C sample loaded with a catalyst above powder in the crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (flow is 100 mL/min), the temperature is raised to 1600 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, the sample is naturally cooled to room temperature, and the sample is taken out.
3. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 180mL/min and the furnace temperature was raised to 1300 c at a heating rate of 5 c/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein, the flow rates of argon, hydrogen and MTS are 400mL/min, 200mL/min and 200mL/min respectively during deposition, the pressure of the reactor is 6.0kPa, and the deposition time is 2 hours. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
Example 4:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.79g/cm 3 Polishing and ultrasonic cleaning with absolute ethanol and deionized water for 25min, and then placing the C/C composite material in an oven at 80 ℃ for 8h until the C/C composite material is dried. And (3) placing the dried C/C composite material in a resistance oxidation furnace at 750 ℃, preserving heat for 10min, taking out a pre-oxidized C/C sample, cooling to room temperature, and weighing for standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: configuration ofAnd (3) placing the C/C sample pre-oxidized in the step (I) into the cobalt nitrate ethanol solution with the concentration of 0.8mol/L, soaking for 3 hours, taking out, and drying for later use. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then weighing 7g of the mixed powder, placing the mixed powder at the bottom of a graphite crucible, hanging a pre-oxidized C/C sample loaded with a catalyst above powder in the crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (the flow is 80 mL/min), the temperature is raised to 1600 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, the sample is naturally cooled to the room temperature, and the sample is taken out.
3. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 180mL/min and the furnace temperature was raised to 1250℃at a heating rate of 5℃per minute. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein, the flow rates of argon, hydrogen and MTS are respectively 500mL/min, 180mL/min and 180mL/min during deposition, the pressure of the reactor is 6.0kPa, and the deposition time is 3 hours. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
Example 5:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.76g/cm 3 Polishing and ultrasonic cleaning with absolute ethanol and deionized water for 40min, and then placing the C/C composite material in an oven at 60 ℃ for 10h until the C/C composite material is dried. And (3) placing the dried C/C composite material in a 950 ℃ resistance oxidation furnace, preserving heat for 10min, taking out a pre-oxidized C/C sample, cooling to room temperature, and weighing for standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing ferric nitrate ethanol solution with the concentration of 0.5mol/L, placing the C/C sample pre-oxidized in the step one into the solution, soaking for 4 hours, taking out, drying and preparingIs used. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and C powder and drying. Then 8g of the mixed powder is weighed and placed at the bottom of a graphite crucible, a pre-oxidized C/C sample loaded with a catalyst is hung above powder in the crucible, and the graphite crucible is placed in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (the flow is 60 mL/min), the temperature is raised to 1500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, the sample is naturally cooled to the room temperature, and the sample is taken out.
3. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 150mL/min and the furnace temperature was raised to 1300 c at a heating rate of 5 c/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein argon is used for deposition
The flow rates of gas, hydrogen and MTS were 400mL/min, 200mL/min and 200mL/min, respectively, the reactor 5 pressure was 5.0kPa, and the deposition time was 3 hours. Stopping introducing gas after deposition, turning off power supply, and cooling
And taking out the sample to room temperature, and obtaining the SiC coating on the surface of the porous layer.
Example 6:
1. C/C composite pre-oxidation treatment: first, siC sand paper is used to make the density of 1.80g/cm 3 C/C of (C)
The composite material was polished and ultrasonically cleaned with absolute ethanol and deionized water for 35min, then placed in an oven at 80 ℃ for 7h until oven dried. Placing the dried C/C composite material in 850 ℃ resistance oxygen
And (3) preserving heat for 8min in a melting furnace, taking out the preoxidized C/C sample, cooling to room temperature, and weighing for standby.
2. Construction of a porous layer of carbon fiber cone@directional SiC nanowire on the surface of the C/C composite material: preparing cobalt nitrate ethanol solution with concentration of 0.6mol/L, and placing the C/C sample pre-oxidized in the step one on the cobalt nitrate ethanol solution
Soaking in the solution for 3h, taking out, and drying for standby. SiO with the mass percentage of 1:0.4:0.5 is prepared 2 And performing ball milling mixing treatment on Si and 5C powder and drying. Then weighing 6g of the mixed powder and placing the mixed powder at the bottom of a graphite crucible, and
suspending a pre-oxidized C/C sample loaded with a catalyst above powder in a crucible, and placing the graphite crucible in a high-temperature reaction chamber of an atmosphere sintering furnace; then under the protection of argon atmosphere (flow is 100 mL/min), the temperature is raised to 1600 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h, the power supply is turned off, the sample is naturally cooled to room temperature, and the sample is taken out.
03. Preparing a SiC coating by an LPCVD method:
and (3) hanging the sample obtained in the step (II) in a deposition area of a vertical deposition furnace, vacuumizing, and controlling the vacuum degree of the atmosphere sintering furnace to be 0.2Pa. Argon was introduced at a flow rate of 180mL/min and the furnace temperature was raised to 1300 c at a heating rate of 5 c/min. When the temperature in the furnace reaches the deposition temperature, the reaction gas hydrogen and the diluent gas argon are introduced, and MTS is brought into the reaction zone by the hydrogen in a bubbling mode for deposition. Wherein the flow rates of argon, hydrogen and MTS are 400mL/min, 150mL/min and 150mL/min respectively during deposition, the reactor pressure is 5.0kPa, and the deposition time is 3h. And stopping introducing gas after the deposition is finished, turning off a power supply, cooling to room temperature, taking out the sample, and obtaining the SiC coating on the surface of the porous layer.
According to the invention, a carbon fiber cone porous layer is constructed on the surface of the C/C composite material through a simple pre-oxidation process, a large-area carbon fiber cone@directional SiC nanowire core-shell structure array is obtained by combining a normal pressure CVD method, and finally the C/C matrix wrapped carbon fiber cone@directional SiC nanowire multi-scale core-shell structure toughened SiC coating is prepared. According to the technical scheme provided by the invention, the matrix-coating multi-scale mechanical linkage structure is effectively designed, the in-situ directional growth nanowire is obtained, the interface combination between the SiC coating and the C/C composite material is improved, the SiC coating is toughened, and a novel technology and a novel method are provided for improving the oxidation/ablation resistance of the C/C composite material. The technical scheme has the advantages of simple operation, controllable process, low raw material cost and good repeatability, and has the potential of developing large-scale industrial productivity.
Claims (4)
1. A method for improving the binding force of a C/C composite substrate and a SiC coating, comprising:
(1) Pre-oxidizing C/C composite material:
firstly, polishing a C/C composite material by using SiC sand paper, ultrasonically cleaning the C/C composite material for 10 to 70 minutes by using absolute ethyl alcohol and deionized water, then placing the C/C composite material in a baking oven at 60 to 100 ℃ for drying for 5 to 24 hours, finally placing the dried C/C composite material in a resistance oxidation furnace at 600 to 1000 ℃, preserving heat for 2 to 10 minutes, and cooling to room temperature;
(2) Construction of a porous layer of carbon fiber cone@oriented SiC nanowire on the surface of the C/C composite material:
soaking the preoxidized C/C composite material in an ethanol solution of a metal salt catalyst with the concentration of 0.1-2 mol/L to load the metal salt catalyst, placing the preoxidized C/C composite material loaded with the metal salt catalyst above powder, raising the temperature to 1200-1800 ℃ under the protection of argon atmosphere, preserving heat for 0.5-10 h, and naturally cooling to room temperature, wherein the powder is SiO with the mass percentage of 1:0.1-0.6:0.2-0.8 2 A mixture of Si, C powders, wherein the metal salt used as a catalyst in the ethanol solution of the metal salt catalyst is selected from ferric nitrate, cobalt nitrate, nickel nitrate, ferrous sulfate, cobalt sulfate, nickel sulfate, ferric chloride, cobalt chloride or nickel chloride;
(3) Preparing a SiC coating by low-pressure chemical vapor deposition:
and (3) taking hydrogen as a reaction gas and argon as a diluent gas at 900-1500 ℃, and taking methyl trichlorosilane into the hydrogen to deposit on the C/C composite material after the second step, wherein the pressure of a reaction area is 3-10 kPa, the deposition time is 0.5-10 h, and the flow rates of the argon, the hydrogen and the methyl trichlorosilane are respectively 150-500 mL/min, 300-800 mL/min and 300-800 mL/min during the deposition, cooling to room temperature after the deposition is finished, and obtaining the SiC coating on the surface of the porous layer.
2. The method of claim 1, wherein the pre-oxidized C/C composite is immersed in the ethanol solution of the metal salt catalyst for a period of 2 to 24 hours.
3. The method according to claim 1, wherein the temperature rising rate to 1200 to 1800 ℃ in the step (2) is 5 to 10 ℃/min.
4. The method according to claim 1, wherein the flow rate of argon in the step (2) is 10 to 200mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211627507.0A CN116003164B (en) | 2022-12-16 | 2022-12-16 | Method for improving binding force between C/C composite material matrix and SiC coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211627507.0A CN116003164B (en) | 2022-12-16 | 2022-12-16 | Method for improving binding force between C/C composite material matrix and SiC coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116003164A CN116003164A (en) | 2023-04-25 |
| CN116003164B true CN116003164B (en) | 2024-01-30 |
Family
ID=86037269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211627507.0A Active CN116003164B (en) | 2022-12-16 | 2022-12-16 | Method for improving binding force between C/C composite material matrix and SiC coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116003164B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426577A (en) * | 1990-05-21 | 1992-01-29 | Toshiba Ceramics Co Ltd | Silicon carbide coated carbon product |
| CN105541412A (en) * | 2016-01-27 | 2016-05-04 | 南京工程学院 | Preparation method of SiC nanowire-toughened SiC ceramic coating on surface of C/C composite |
| CN106083206A (en) * | 2016-06-14 | 2016-11-09 | 陕西科技大学 | A kind of internally coated preparation method of carbon/carbon compound material SiC |
| CN107059129A (en) * | 2017-04-05 | 2017-08-18 | 西北工业大学 | Co-precipitation and the preparation method of thermal evaporation techniques fabricated in situ taper SiC whiskers |
| CN115058885A (en) * | 2022-06-13 | 2022-09-16 | 西北工业大学 | Carbon fiber cloth surface oriented SiC nanowire array and preparation method thereof |
| CN115259159A (en) * | 2022-07-05 | 2022-11-01 | 西北工业大学 | Inverted cone-shaped nitrogen-doped silicon carbide nanowire with high length-diameter ratio and preparation method thereof |
-
2022
- 2022-12-16 CN CN202211627507.0A patent/CN116003164B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426577A (en) * | 1990-05-21 | 1992-01-29 | Toshiba Ceramics Co Ltd | Silicon carbide coated carbon product |
| CN105541412A (en) * | 2016-01-27 | 2016-05-04 | 南京工程学院 | Preparation method of SiC nanowire-toughened SiC ceramic coating on surface of C/C composite |
| CN106083206A (en) * | 2016-06-14 | 2016-11-09 | 陕西科技大学 | A kind of internally coated preparation method of carbon/carbon compound material SiC |
| CN107059129A (en) * | 2017-04-05 | 2017-08-18 | 西北工业大学 | Co-precipitation and the preparation method of thermal evaporation techniques fabricated in situ taper SiC whiskers |
| CN115058885A (en) * | 2022-06-13 | 2022-09-16 | 西北工业大学 | Carbon fiber cloth surface oriented SiC nanowire array and preparation method thereof |
| CN115259159A (en) * | 2022-07-05 | 2022-11-01 | 西北工业大学 | Inverted cone-shaped nitrogen-doped silicon carbide nanowire with high length-diameter ratio and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SiC coating toughened by SiC nanowires to protect C/C composites against oxidation;Yanhui Chu et al.;《Ceramics International》;第38卷;第190页左栏第3-4段，右栏第4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116003164A (en) | 2023-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115108852B (en) | Graphite composite material and preparation method and application thereof | |
| WO2020199681A1 (en) | Method for preparing high-performance silicon carbide coating on surface of carbon/carbon composite thermal insulation material | |
| CN108395279B (en) | Method for preparing HfC-SiC complex phase gradient coating by chemical vapor codeposition method | |
| CN109467450B (en) | Ti-containing alloy3SiC2SiC of the interface layerfPreparation method of/SiC composite material | |
| CN113045326B (en) | Preparation method of modified carbon/carbon composite material | |
| CN106966703B (en) | Alumina fiber reinforced alumina ceramic containing interface phase and preparation method thereof | |
| CN109485423B (en) | Preparation method of SiC nanowire toughened HfC-SiC complex phase coating by chemical vapor codeposition | |
| CN113024281B (en) | Silicon carbide/graphene bionic laminated coating and preparation method thereof | |
| CN110357635A (en) | A method of improving carbon-based or ceramic matric composite surface oxidation-resistant coating bond strength | |
| CN109704776B (en) | Directional heat conduction channel construction method of high heat conduction diamond modified silicon carbide ceramic matrix composite material | |
| CN112341233A (en) | Multi-element single-phase ultra-high temperature ceramic TaxHf1-xPreparation method of C modified carbon/carbon composite material | |
| CN102126859A (en) | Method for preparing bamboo-shaped SiC nanowire-toughened HfC ceramic | |
| CN111485220A (en) | SiC nanowire toughened chemical vapor deposition ZrC coating and preparation method thereof | |
| CN112851387B (en) | Method for preparing silicon carbide coating on surface of carbon-carbon composite material | |
| CN110372408A (en) | A kind of ceramic fibre toughening CVD silicon carbide composite material and preparation method and application | |
| CN104150938B (en) | The preparation method of one dimension hafnium carbide HfC material modification carbon/carbon composite | |
| CN113321522B (en) | SiC nanowire modified SiC for in-situ growthfPreparation method and application of/SiC ceramic matrix composite material | |
| CN110042468A (en) | A kind of preparation method of micrometer silicon carbide zirconium whisker | |
| CN113045325B (en) | Preparation method of high-strength carbon/carbon-silicon carbide composite material | |
| CN116003164B (en) | Method for improving binding force between C/C composite material matrix and SiC coating | |
| CN113603509A (en) | Preparation method of oxidation-resistant ablation coating on surface of C/C composite material | |
| CN113106416A (en) | Ablation-resistant ZrC/SiC multilayer alternating coating and preparation method thereof | |
| CN115894085B (en) | Composite ceramic coating material and preparation method and application thereof | |
| CN115536413B (en) | Multilayer core-shell structure nanowire toughening chemical vapor deposition SiC coating and preparation method thereof | |
| CN108546142B (en) | CfPreparation method of-HfCnw micro-nano multi-scale strengthening and toughening carbon-based composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |